Ink-jet recording method and ink composition set

ABSTRACT

An ink composition set including an ink composition A containing at least a colorant and an interior curable photopolymerization initiator, and an ink composition B containing at least a polymerizable compound, a surface curable photopolymerization initiator and a polymerization accelerator, and an ink-jet recording method using the ink composition set.

FIELD OF THE INVENTION

The present invention relates to an ink-jet recording method and an inkcomposition set, and more particularly, it relates to such an ink-jetrecording method and an ink composition set that an ink coated film canbe sufficiently cured even in the case where a two-component inkcomposition is printed on a recording medium to a thick film, or in thecase where an ink composition having a high colorant content is printed.

BACKGROUND OF THE INVENTION

In the ink-jet recording method, small droplets of an ink compositionare ejected and attached to a recording medium, such as paper, to effectprinting. The ink-jet recording method has such a characteristic featurethat an image having high resolution with high quality can be printed ata high speed. The ink composition used in the ink-jet recording methodgenerally contains an aqueous solvent as a major component and alsocontains a colorant component and a moistening agent, such as glycerin,for preventing clogging.

In the case where the ink-jet recording method is applied to paper andfabrics to which the aqueous ink composition is difficult to penetrate,or applied to metal and plastic materials to which the aqueous inkcomposition does not penetrate, for example, a plate or a film made of aresin, such as a phenol resin, a melamine resin, a vinyl chloride resin,an acrylic resin and a polycarbonate resin, it is required that the inkcomposition or a reaction liquid contains a component capable of stablyfixing the colorant component to the recording medium.

According to the requirement, an ultraviolet ray-curable ink for ink-jetrecording containing a colorant, an ultraviolet curing agent (i.e., apolymerizable compound) and a polymerization (photopolymerization)initiator is disclosed (for example, in Patent Document 1). There hasbeen stated that the ink is prevented from causing blur on a recordingmedium to improve image quality. The ultraviolet ray-curable inkdisclosed in Patent Document 1 is an one-component ink composition.

However, in a step of curing a one-component ultraviolet ray-curable inkcomposition by irradiating with an ultraviolet ray after attaching theink composition to a recording medium, such a phenomenon is oftenobserved that the only outside (surface) of the ink coated film iscured, but the interior thereof remains as a liquid uncured. This isbecause an ultraviolet ray is absorbed only by the surface of the coatedfilm but fails to reach the interior thereof. There are some cases onthe other hand that only the interior is cured, but the surface is notcured. This is a phenomenon that is often observed when thepolymerization rate is low, and it is considered that this is because ofpolymerization inhibition due to permeation of oxygen from the surface.

In order to avoid the problems, such a measure is often employed thatplural kinds of photopolymerization initiators are used in combination.Specifically, a photopolymerization initiator having a high initiatorefficiency (which is suitable for surface curing and can suppresspolymerization inhibition due to permeation of oxygen) and aphotopolymerization initiator suitable for interior curing having aphotobleaching effect (in which after cleaving the photopolymerizationinitiator by absorbing light, the residue of the initiator afterdecomposition does not absorb an ultraviolet ray to fail to prevent anultraviolet ray from penetrating into the interior) are used incombination.

Patent Document 1; U.S. Pat. No. 5,623,001

Even in the case where the plural photopolymerization initiators arecombined, however, where are some cases where an ultraviolet ray isliable to be absorbed, reflected or scattered by a colorant when aone-component ink composition is coated to a thick film on a recordingmedium, or an ink composition having a high colorant content is coated.Accordingly, an ultraviolet ray is difficult to penetrate into theinterior of the ink coated film to prevent polymerization reaction fromproceeding, which brings about insufficient curing. In the case wherethe addition amount of the photopolymerization initiator is increasedtherefore, there arises such a vicious cycle that an ultraviolet ray isexcessively absorbed in the ink coated film to prevent an ultravioletray from penetrating into the interior, which brings about curingfailure.

In the invention, the problems are solved by using two or more kinds ofultraviolet ray-curable ink compositions in combination. Specifically,one of the ink compositions contains a photopolymerization initiatorsuitable for interior curing having a photobleaching effect (in whichafter cleaving the photopolymerization initiator by absorbing light, theresidue of the initiator after decomposition does not absorb anultraviolet ray to fail to prevent an ultraviolet ray from penetratinginto the interior) in a large amount, and the other ink compositioncontains a photopolymerization initiator having a high initiatorefficiency (which is suitable for surface curing and can suppresspolymerization inhibition due to permeation of oxygen) and apolymerization accelerator containing fine particles havingpolymerizable functional groups on the surface thereof. The use of theink compositions in combination solves the aforementioned problems ofcuring failure.

SUMMARY OF THE INVENTION

The invention is to solve the problems associated with the conventionalart, i.e., an object of the invention is to provide such an ink-jetrecording method and an ink composition set that even in the case wherea thick film is printed on a recording medium, or in the case where anink composition having a high colorant content is printed, both thesurface and the interior of the recorded image on the recording mediumcan be sufficiently cured.

Other objects and effects of the invention will become apparent from thefollowing description.

As a result of earnest investigations made by the inventors, theaforementioned objects of the invention were attained by the followingconstitutions to complete the invention.

The invention includes the following constitutions.

(1) An ink-jet recording method comprising steps of:

preparing an ink composition set comprising an ink composition Acomprising at least a colorant and an interior curablephotopolymerization initiator, and an ink composition B comprising atleast a polymerizable compound, a surface curable photopolymerizationinitiator and a polymerization accelerator;

attaching the ink composition A and the ink composition B to a recordingmedium; and

irradiating the compositions with an ultraviolet ray to form an imagethrough ultraviolet ray curing.

(2) The ink-jet recording method according to (1) above, wherein thepolymerization accelerator comprises fine particles having apolymerizable functional group.

(3) The ink-jet recording method according to (1) above, wherein theinterior curable photopolymerization initiator contained in the inkcomposition A comprises an acylphosphine oxide as a major componentcontained in an amount of 60% by weight or more based on thephotopolymerization initiator in the ink composition A.

(4) The ink-jet recording method according to (1) above, wherein thesurface curable photopolymerization initiator contained in the inkcomposition B comprises an α-aminoketone as a major component containedin an amount of 60% by weight or more based on the photopolymerizationinitiator in the ink composition B.

(5) The ink-jet recording method according to (1) above, wherein thecolorant contained in the ink composition A is a pigment.

(6) An ink composition set comprising an ink composition A comprising atleast a colorant and an interior curable photopolymerization initiator,and an ink composition B comprising at least a polymerizable compound, asurface curable photopolymerization initiator and a polymerizationaccelerator.

According to the ink-jet recording method of the invention, the ink tobe used is divided into two liquids. A colorant and aphotopolymerization initiator suitable for interior curing areincorporated into one of them (ink composition A), and a polymerizablecompound, a photopolymerization initiator suitable for surface curingand a polymerization initiator are incorporated into the other (inkcomposition B). Thus, an ink composition set comprising the above inkcomposition A and the above ink composition B is used, and immediatelyafter ejecting the ink composition A onto a recording medium, the inkcomposition B is ejected thereto, followed by irradiating with anultraviolet ray. Consequently, the ink composition A forms a colorantlayer on the recording medium, and the ink composition B forms atransparent protective layer on the colorant layer As for the inkcomposition B for forming the transparent protective layer, aphotopolymerization initiator suitable for surface curing is used, aproportion of a surface curing initiator is made larger than that of aninterior curing initiator, and a polymerization accelerator containingfine particles having polymerizable functional groups introduced ontothe surface thereof is used. Accordingly, the polymerization rate isimproved, and polymerization inhibition due to permeation of oxygen issuppressed, whereby the surface of the ink coated film can be rapidlycured, and the amount of the initiator can be decreased to a minimumlevel.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view showing an ink-jet recording apparatus thatis preferably used in the ink-jet recording method of the invention.

The reference numerals used in the drawings denote the followings,respectively.

1 a: recording head

1 b: recording head

2 a: ink tank

2 b: ink tank

3: tube

4: carriage

5: motor

6: timing belt

7: recording medium

8: platen

9: guide

10: cap

11: aspiration pump

12: tube

13: waste ink tank

14: heater

15: ultraviolet ray irradiating means

DETAILED DESCRIPTION OF THE INVENTION

The ink-jet recording method of the invention as well as the inkcomposition set of the invention will be described in detail below.

The ink-jet recording method of the invention uses an ink compositionset comprising two liquids, i.e., an ink composition A containing atleast a colorant and an interior curable photopolymerization initiator,and an ink composition B containing at least a polymerizable compound, asurface curable photopolymerization initiator and a polymerizationaccelerator.

The number of the ink composition A may be determined by the imageforming process. For example, in the case where the method is applied toa recording apparatus for forming a full color image with four colors,four kinds of compositions having four colors, yellow, magenta, cyan andblack, respectively, are used. In addition, such an ink composition mayalso be used depending on necessity as a light-color ink composition oflight magenta, light cyan or gray, a medium color or special color inkcomposition of red, green, blue, orange or violet, and a special inkcomposition of white or metallic color.

In the following description, the ink composition A is sometimesreferred to as a “white ink composition”, “color ink composition” orsimply “ink composition” since it contains a colorant, and the inkcomposition B is sometimes referred to as a “transparent inkcomposition” since it contains no colorant.

The ink composition A used in the ink-jet recording method of theinvention contains a photopolymerization initiator in such a manner thatthe interior curing property is increased, and the ink composition Bcontains a photopolymerization initiator in such a manner that thesurface curing property is increased.

The photopolymerization initiator contained in the ink compositions Aand B is, for example, a compound that forms a radical or an ion throughabsorption of an ultraviolet ray or a visible ray in a region of aboutfrom 200 to 450 nm to initiate polymerization of a polymerizablecompound.

Representative examples of the photopolymerization initiator used in theink compositions A and B of the invention, referring toradical-generating ones, include benzoin methyl ether, benzoin ethylether, isopropyl benzoin ether, isobutyl benzoin ether,1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, benzyl,diethoxyacetophenone, benzophenone, chlorothioxanthone,2-chlorothioxanthone, isorpropylthioxanthone, 2-methylthioxanthone,polyphenyl polychloride and hexachlorbenzene. Preferred examples thereofinclude isobutyl benzoin ether and1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime.

Commercially available photopolymerization initiators can also be used,such as those available under the trade names, e.g., Vicure 10 and 30(all produced by Stauffer Chemical Co.), Irgacure 127, 184, 500, 651,2959, 907, 369, 379, 754, 1700, 1800, 1850 and 819, OXE01, Darocur 1173,TPO and ITX (all produced by Ciba Specialty Chemicals, Inc.), QuantacureCTX (produced by Aceto Chemical Co.), Kayacure DETX-S (produced byNippon Kayaku Co., Ltd.) and ESACURE KIP150 (produced by Lamberti).

In order that the ink composition A used in the ink-jet recording methodof the invention contains a photopolymerization initiator to have highinterior curing property as having been described, it is preferred, forexample, that an acylphosphine oxide compound is used as a majorcomponent the photopolymerization initiator contained in the inkcomposition A, and the amount of the acylphosphine oxide compound is 60%by weight or more based on the total amount of the photopolymerizationinitiator contained in the ink composition A.

Examples of the acylphosphine oxide compound include those havingabsorption in a region of a wavelength of 365 nm or more, such asbis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, which is availableunder a trade name of Irgacure 819 (produced by Ciba SpecialtyChemicals, Inc.).

In order that the ink composition B used in the ink-jet recording methodof the invention contains a photopolymerization initiator to have highsurface curing property, it is preferred, for example, that anα-aminoketone compound is used as a major component thephotopolymerization initiator contained in the ink composition B, andthe amount of the α-aminoketone compound is 60% by weight or more basedon the total amount of the photopolymerization initiator contained inthe ink composition B.

Examples of the α-aminoketone compound include those having absorptionin a region of a wavelength of 365 nm or more, such as2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butaone-1, which isavailable under a trade name of Irgacure 369 (produced by Ciba SpecialtyChemicals, Inc.).

While the colorant contained in the ink composition A used in theink-jet recording method of the invention may be ether a dye or apigment, a pigment dispersed in the ink composition is advantageousrather than a dye dissolved in the ink composition in the case where thecolorant component in the ink composition is suppressed from penetratingby such a function of the ink composition as insolubilization andthickening, and a pigment is preferably used from the standpoint ofdurability of printed matters.

Examples of the dye that can be used in the invention include variousdyes that are generally used for ink-jet recording, such as a directdye, an acidic dye, an edible dye, a basic dye, a reactive dye, adisperse dye, a vat dye, a soluble vat dye and a reactive disperse dye.

The pigment used in the invention may be an inorganic pigment and anorganic pigment without any particular limitation.

Examples of the inorganic pigment include titanium oxide, iron oxide andcarbon black produced by the known process, such as the contact process,the furnace process and the thermal process. Examples of the organicpigment include an azo pigment (such as an azo lake pigment, aninsoluble azo pigment, a condensed azo pigment and a chelate azopigment), a polycyclic pigment (such as a phthalocyanine pigment, aperylene pigment, a perynone pigment, an anthraquinone pigment, aquinacridone pigment, a dioxadine pigment, a thioindigo pigment, anisoindolinone pigment and a quinophthalone pigment), a dye chelate (suchas a basic dye chelate and an acidic dye chelate), a nitro pigment, anitrso pigment and aniline black.

Specific examples of the pigment include carbon black, such as No. 2300,No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100 and No.2200B, all produced by Mitsubishi Chemical Corp., Raven 5750, Raven5250, Raven 5000, Raven 3500, Raven 1255 and Raven 700, all produced byColumbian Chemicals Company, Regal 400R, Regal 330R, Regal 660R, MogulL, Mogul 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000,Monarch 1100, Monarch 1300 and Monarch 1400, all produced by Cabot Oil &Gas Corp., and Color Black FW1, Color Black FW2, Color Black FW2V, ColorBlack FW18, Color Black FW200, Color Black S150, Color Black S160, ColorBlack S170, Printex 35, Printex 35U, Printex 35V, Printex 140U, SpecialBlack 6, Special Black 5, Special Black 4A and Special Black 4, allproduced by Degussa AG.

Examples of the pigment used in an yellow ink include C.I. PigmentYellow 1, 2, 3, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109,110, 114, 128, 129, 138, 150, 151, 154, 155, 180 and 185.

Examples of the pigment used in a magenta ink include C.I. Pigment Red5, 7, 12, 48(Ca), 48(Mn), 57(Ca), 57:1, 112, 122, 123, 168, 184, 202 and209, and C.I. Pigment Violet 19.

Examples of the pigment used in a cyan ink include C.I. Pigment Blue 1,2, 3, 15:3, 15:4, 60, 16 and 22.

According to a preferred embodiment of the invention, the pigmentpreferably has an average particle diameter in a range of from 10 to 200nm, and more preferably in a range of from 50 to 150 nm.

The addition amount of the colorant in the ink composition A ispreferably in a range of about from 0.1 to 25% by weight, and morepreferably in a range of from 0.5 to 15% by weight.

In a preferred embodiment of the invention, the pigment is dispersed inan aqueous medium with a dispersant or a surfactant to obtain a pigmentdispersion liquid, which is then added to the ink composition A.Preferred examples of the dispersant include those dispersants that areordinarily used for preparing a pigment dispersion liquid, such as apolymer dispersant. It is apparent to a skilled person in the art thatthe dispersant and the surfactant contained in the pigment dispersionliquid also function as a dispersant and a surfactant in the inkcomposition A.

Specific examples of the dispersant include a polymer dispersant, suchas polyacrylic acid, an acrylic acid-styrene copolymer, polyester,polyurethane, polyvinyl chloride, a vinyl chloride-vinyl acetatecopolymer, vinyl chloride-modified polyacrylic acid,polyoxyalkylene-added polyalkyleneamine and polyvinyl butyral, asilicone surfactant, such as polyester-modified polydimethylsiloxane andpolyether-modified polydimethylsiloxane, an acetylenediol surfactant,and a sorbitan surfactant.

The ink composition A of the invention may contain an aqueous solvent,and may also contain, as arbitrary components, a resin emulsion, aninorganic oxide colloid, a wetting agent, a pH adjusting agent, anantiseptic and an antifungal agent.

The polymerizable compound contained in the ink composition B used inthe ink-jet recording method of the invention is not particularlylimited as far as it is a compound capable of being polymerized with aradical or an ion formed from the photopolymerization initiator.

Examples of the polymerizable compound contained in the ink compositionof the invention include a monomer. The monomer used in the invention isreferred to as a photopolymerizable monomer, which includes amonofunctional monomer, a bifunctional monomer and a polyfunctionalmonomer, examples of which are given below. The monomers to be usedgenerally have a molecular weight in a range of about from 100 to 3,000,and preferably in a range of about from 100 to 2,000.

(Monofunctional Monomer)

Examples of the monofunctional monomer include(2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate,(2-methyl-2-isobutyl-1,3-dioxolan-4-yl)methyl acrylate, phenoxyethylacrylate, isobornyl acrylate, N-vinylformamide, methoxydiethylene glycolmonoacrylate, acryloylmorpholine, lauryl methacrylate, allyl glycol,2-hydroxyethyl methacrylate, cyclohexyl methacrylate, oxetanemethacrylate, N-vinylcarbazole, N-vinylacetamide, N-vinylpyrrolidone andN-vinylcaprolactam.

(Bifunctional Monomer)

Examples of the bifunctional monomer include ethylene glycoldimethacrylate, diethylene glycol diacrylate, diethylene glycoldimethacrylate, tripropylene glycol diacrylate, 1,9-nonanedioldiacrylate, polyethylene glycol #400 diacrylate, tetraethylene glycoldimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanedioldimethacrylate, neopentyl glycol diacrylate, neopentyl glycoldimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane andhydroxybioperinate ester of neopentyl glycol acrylate.

(Polyfunctional Monomer)

Examples of the polyfunctional monomer include trimethylolpropanetriacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EOadduct triacrylate, trimethylolpropane EO-modified triacrylate,trimethylolpropane PO adduct triacrylate, glycerin EO adducttriacrylate, glycerin PO adduct triacrylate, pentaerythritoltriacrylate, dipentaerythritol hexaacrylate,(2,2,2-triacyloyloxymethyl)ethyl hydrogen phthalate anddipentaerythritol polyacrylate.

Among these monomers, preferred examples thereof includeacryloylmorpholine, phenoxyethyl acrylate and N-vinylformamide (whichare monofunctional monomers), tripropylene glycol diacrylate (which is abifunctional monomer), and (2,2,2-triacyloyloxymethyl)ethyl hydrogenphthalate, dipentaerythritol polyacrylate, glycerin EO adducttriacrylate and trimethylolpropane EO-modified triacrylate (which arepolyfunctional monomers).

The polymerization accelerator contained in the ink composition B usedin the ink-jet recording method of the invention is preferably apolymerization accelerator containing an amine compound. The aminecompound is not particularly limited, and an aminobenzoate derivative ispreferred since it is free of problem in odor and secures curing of theink composition. This is because an aminobenzoate derivative suppressespolymerization inhibition due to oxygen.

Preferred examples of the aminobenzoate derivative include those havingno absorption in a wavelength range of 350 nm or more. Examples of theaminobenzoate derivative include, while not limited, ethyl-4-dimethylaminobenzoate and 2-ethylhexyl-4-dimethyl aminobenzoate, which arecommercially available under a trade name, Darocur EHA and EDB (allproduced by Ciba Specialty Chemicals, Inc.).

Other examples of the polymerization initiator include fine particleshaving polymerizable functional groups.

While not completely clear, it is expected that the mechanism ofpolymerization acceleration by the fine particles having polymerizablefunctional groups is as follows. A radical formed by cleavage of thephotopolymerization initiator through absorption of an ultraviolet rayis stabilized by trapping on the surface of the fine particles, andeasily starts polymerization reaction with the polymerizable groups onthe surface of the fine particles and the monomer adsorbed on thesurface of the fine particles.

The fine particles having polymerizable functional groups are notparticularly limited, and examples thereof include those generallyreferred to as a body pigment, such as an inorganic compound, e.g.,silica, alumina, titania and calcium oxide, and transparent ones, suchas silica and alumina, are particularly preferably used.

The polymerizable functional group that the fine particles have is notparticularly limited, and examples thereof include an acryloyl group anda methacryloyl group, and also include a polymerizable functional grouphaving one or more double bonds.

The fine particles are not particularly limited in size, and theparticle diameter thereof is preferably from 10 to 100 nm.

The method for preparing the fine particles having polymerizablefunctional groups is not particularly limited, and examples thereofinclude such a method that silica fine particles having a large amountof hydroxyl groups are prepared through sol-gel reaction of a silanecompound, such as tetraethoxysilane, and the hydroxyl groups are reactedwith a compound (silane coupling agent) capable of adding apolymerizable functional group thereto.

The content of the fine particles having polymerizable functional groupsin the ink composition B in the invention is not particularly limited,and can be appropriately determined depending on relationship among themode and conditions of use and the viscosity and polymerization propertyof the ink composition. The content thereof is preferably 10% by weightor less based on the total amount of the ink composition.

The ink composition B of the invention may contain an aqueous solvent,and may also contain, as arbitrary components, a polyvalent metallicsalt, a polyallylamine or a derivative thereof, a wetting agent, a pHadjusting agent, an antiseptic and an antifungal agent.

The ink compositions A and B of the invention preferably has adifference in viscosity at 25° C. of 2 mPa·s or less from the standpointof handleability in ink-jet recording.

Both the ink compositions A and B of the invention are preferablynon-solvent ink compositions containing no organic solvent.

In one embodiment of the ink-jet recording method of the invention, theink composition A is ejected onto a recording medium, and immediatelyafter that, the ink composition B is ejected thereto, followed byirradiating with an ultraviolet ray.

The irradiation amount of an ultraviolet ray is generally from 10 to10,000 mJ/cm², and preferably from 50 to 6,000 mJ/cm². The curingreaction can proceed sufficiently with the irradiation amount of anultraviolet ray in the aforementioned range.

The irradiation of an ultraviolet ray may be carried out with variouslamps, such as a metal halide lamp, a xenon lamp, a carbon arc lamp, alow pressure mercury lamp and a high pressure mercury lamp. For example,a commercially available lamp, such as H Lamp, D Lamp and V Lamp,produced by Fusion System Corp., can be used.

The irradiation of an ultraviolet ray may also be carried out by usingan ultraviolet ray emitting semiconductor device, such as an ultravioletray emitting diode (ultraviolet ray LED) and an ultraviolet raysemiconductor laser,

In the ink-jet recording method of the invention, the recording mediumhaving the ink compositions may be heated before, simultaneously with orafter irradiation with an ultraviolet ray. Examples of the heatingoperation include a method of heating the recording medium by contactingthe recording medium with a heat source, and a method of heating therecording medium without contact, e.g., irradiation with an infrared rayor microwave (electromagnetic wave having a maximum wavelength at around2,450 MHz) and blowing with hot air.

An example of a recording apparatus for practicing the ink-jet recordingmethod of the invention will be described.

FIG. 1 is a perspective view showing an ink-jet recording apparatushaving a means for attaching the ink-jet compositions A and B to arecording medium, a driving system for driving the means, a means forconveying the recording medium, a means for irradiating the recordingmedium with an ultraviolet ray, a means for heating the recordingmedium, and a cleaning means.

Recording heads 1 a and 1 b are connected to an ink tank 2 a containingthe ink composition A and an ink tank 2 b containing the ink compositionB, respectively, and move in a direction shown by the arrow A along acarriage 4 with a timing belt 6 driven by a motor 5. During themovement, the ink composition A is ejected from a nozzle surface of therecording head 1 a and attached to a recording medium 7 placed on aposition facing the recording head 1 a with a platen 8 and a guide 9.The recording medium 7 is then conveyed in a paper conveying directionshown by the arrow B at a prescribed conveying amount, during which therecording heads 1 a and 1 b move a direction opposite to the arrow A inthe figure and return to the left-end position of the recording medium7. The ink composition B is then ejected from a nozzle surface of therecording head 1 b to effect printing on the recording medium having theink composition A attached. The recording medium 7 thus printed isfurther conveyed in the paper conveying direction shown by the arrow Bat a prescribed conveying amount and subjected to ultravioletirradiation with an ultraviolet ray irradiating means 15 and heatingwith a heater 14. On the surface of the recording medium 7 having beensubjected to the treatments, the ink compositions A and B undergo curingreaction to fix the colorant onto the recording medium 7. The recordingmedium 7 having been printed is further conveyed in the paper conveyingdirection shown by the arrow B. The apparatus has a cap 10 connected toan aspiration pump 11, by which a cleaning operation is effected. Theink compositions aspirated are stored in a waste ink tank 13 through atube 12.

The ink-jet recording method of the invention can be applied to printingon a non-absorptive recording material, such as metal, glass andplastics, production of a color filter, and marking on a printed circuitboard.

EXAMPLE

The present invention will be illustrated in greater detail withreference to the following Examples, but the invention should not beconstrued as being limited thereto.

Examples 1 to 8, Reference Examples 1 to 8, and Comparative Examples 1to 24

Examples 1 to 8, Reference Examples 1 to 8, and Comparative Examples 1to 24 shown in Table 2 below are all examples using the ink compositionsets containing white ink compositions (W1 to W4, ink composition A) andtransparent ink compositions (T1 to T6, ink composition B). Irgacure 819(an interior curable photopolymerization initiator, produced by CibaSpecialty Chemicals, Inc.) and Irgacure 369 (a surface curablephotopolymerization initiator, produced by Ciba Specialty Chemicals,Inc.) are used as photopolymerization initiators mixed with the inkcompositions A and B, but the invention is not limited thereto.

Production Process of Titanium Dioxide Fine Particles

Titanium-containing ore was dissolved in sulfuric acid to obtain atitanium sulfate solution. To hydrated titanium oxide obtained byhydrolysis of the titanium sulfate solution, 0.50 part by weight ofammonium phosphate, 0.30 part by weight of potassium sulfate and 0.30part by weight of aluminum sulfate were added per 100 parts by weight ofTiO₂, and the hydrated titanium oxide was heated to a producttemperature of 1,020° C. in a laboratory rotary muffle furnace. Titaniumdioxide fine particles thus formed were cooled to room temperature, andobservation thereof with a transmission electron microscope revealedthat they had an anatase structure and a primary particle diameter of0.13 μm. 1,500 g of the titanium dioxide fine particles having beensurface-treated and 1,000 g of isopropyl alcohol (hereinafter, referredto as IPA) were mixed to obtain slurry, and the slurry was dispersed for2 hours in a sand mill (produced by Yasukawa Manufacturing Co., Ltd.) inwhich zirconium beads were charged in an amount 1.5 times the slurry.The beads were removed from the slurry to obtain a 60% by weight IPAdispersion liquid (A) of titanium dioxide fine particles (B) used in awhite ink for ink-jet recording.

1. White Ink Composition (Ink Composition A: Ink Composition Containingat Least Colorant and Photopolymerization Initiator)

1) White Ink Composition 1 (W1) (Ink Composition A) N-Vinylformamide 60parts by weight (Beamset 770, produced by Arakawa Chemical Industries,Ltd.) Tripropylene glycol diacrylate 30 parts by weight (Aronix M-220,produced by Toagosei Co., Ltd.) Irgacure 819 2.5 parts by weight(produced by Ciba Specialty Chemicals, Inc.) Irgacure 369 0.5 part byweight (produced by Ciba Specialty Chemicals, Inc.) Darocur EHA 1 partby weight (produced by Ciba Specialty Chemicals, Inc.) Titanium dioxidefine particles (B) 6 parts by weightProduction Process of White Ink Composition 1

140 parts by weight of Beamset 770 and 100 parts by weight of the IPAdispersion liquid (A) were placed in a 300-mL round bottom flask, fromwhich IPA was distilled out by using a rotary evaporator, to obtain amonomer dispersion liquid (C) containing 30% by weight of the titaniumdioxide fine particles (B).

20 parts by weight of the monomer dispersion liquid (C) was placed in alight-shielded vessel, to which 46 parts by weight of Beamset 770, 30parts by weight of Aronix M-220, 2.5 parts by weight of Irgacure 819,0.5 part by weight of Irgacure 369 and 1 part by weight of Darocur EHAwere added, followed by mixing and stirring with a magnetic stirrer for1 hour, to prepare a white ink composition 1 (W1).

2) White Ink Composition 2 (W2) (Ink Composition A): N-Vinylformamide 60parts by weight (Beamset 770, produced by Arakawa Chemical Industries,Ltd.) Tripropylene glycol diacrylate 29 parts by weight (Aronix M-220,produced by Toagosei Co., Ltd.) Irgacure 819 4.0 parts by weight(produced by Ciba Specialty Chemicals, Inc.) Darocur EHA 1 part byweight (produced by Ciba Specialty Chemicals, Inc.) Titanium dioxidefine particles (B) 6 parts by weightProduction Process of White Ink Composition 2

20 parts by weight of the monomer dispersion liquid (C) was placed in alight-shielded vessel, to which 46 parts by weight of Beamset 770, 29parts by weight of Aronix M-220, 4.0 parts by weight of Irgacure 819 and1 part by weight of Darocur EHA were added, followed by mixing andstirring with a magnetic stirrer for 1 hour, to prepare a white inkcomposition 2 (W2).

3) White Ink Composition 3 (W3) (Ink Composition A): N-Vinylformamide 60parts by weight (Beamset 770, produced by Arakawa Chemical Industries,Ltd.) Tripropylene glycol diacrylate 29 parts by weight (Aronix M-220,produced by Toagosei Co., Ltd.) Irgacure 369 4.0 parts by weight(produced by Ciba Specialty Chemicals, Inc.) Darocur EHA 1 part byweight (produced by Ciba Specialty Chemicals, Inc.) Titanium dioxidefine particles (B) 6 parts by weightProduction Process of White Ink Composition 3

20 parts by weight of the monomer dispersion liquid (C) was placed in alight-shielded vessel, to which 46 parts by weight of Beamset 770, 29parts by weight of Aronix M-220, 4.0 parts by weight of Irgacure 369 and1 part by weight of Darocur EHA were added, followed by mixing andstirring with a magnetic stirrer for 1 hour, to prepare a white inkcomposition 3 (W3).

4) White Ink Composition 4 (W4) (Ink Composition A): N-Vinylformamide 60parts by weight (Beamset 770, produced by Arakawa Chemical Industries,Ltd.) Tripropylene glycol diacrylate 29 parts by weight (Aronix M-220,produced by Toagosei Co., Ltd.) Irgacure 819 2.0 parts by weight(produced by Ciba Specialty Chemicals, Inc.) Irgacure 369 2.0 parts byweight (produced by Ciba Specialty Chemicals, Inc.) Darocur EHA 1 partby weight (produced by Ciba Specialty Chemicals, Inc.) Titanium dioxidefine particles (B) 6 parts by weightProduction Process of White Ink Composition 4

20 parts by weight of the monomer dispersion liquid (C) was placed in alight-shielded vessel, to which 46 parts by weight of Beamset 770, 29parts by weight of Aronix M-220, 2.0 parts by weight of Irgacure 819,2.0 parts by weight of Irgacure 369 and 1 part by weight of Darocur EHAwere added, followed by mixing and stirring with a magnetic stirrer for1 hour, to prepare a white ink composition 4 (W4).

2. Transparent Ink Composition (Ink Composition B: Ink CompositionContaining at Least Polymerizable Compound, PhotopolymerizationInitiator, and Polymerization Accelerator)

1) Transparent Ink Composition 1 (T1): N-Vinylformamide 59 parts byweight (Beamset 770, produced by Arakawa Chemical Industries, Ltd.)Tripropylene glycol diacrylate 20 parts by weight (Aronix M-220,produced by Toagosei Co., Ltd.) Glycerin ethylene oxide adduct 10 partsby weight triacrylate (NK Ester A-Gly-3E, produced by Shin-nakamuraChemical Corp.) Irgacure 819 1.5 parts by weight (produced by CibaSpecialty Chemicals, Inc.) Irgacure 369 2.5 parts by weight (produced byCiba Specialty Chemicals, Inc.) Darocur EHA 1.0 part by weight (producedby Ciba Specialty Chemicals Inc.) Polymerizable fine particles 1 6.0parts by weightProduction Process of Polymerizable Fine Particles 1

88.1 parts by weight of silica sol IPA-ST (an isopropyl alcohol (IPA)dispersion liquid having a silica concentration of 30% by weight,produced by Nissan Chemical Industries, Ltd.) was placed in a 200-mLconical flask, to which 7.9 parts by weight of a silane coupling agent(Sila-Ace S710, produced by Chisso Corp.) was added. Under stirring witha magnetic stirrer, 4 parts by weight of hydrochloric acid having aconcentration of 0.05 mol/L was added, and reaction was carried out atroom temperature under stirring for 24 hours. As a result, an IPAdispersion liquid A containing polymerizable fine particles 1.

Production Process of Transparent Ink Composition 1

70 parts by weight of N-vinylformamide (hereinafter, referred to as NVF)and 100 parts by weight of the dispersion liquid A were placed in a300-mL round bottom flask, from which IPA was distilled out by using arotary evaporator, to obtain a monomer solution B containing 30% byweight of the polymerizable fine particles 1.

20 parts by weight of the monomer solution B was placed in a 100-mLlight-shielded sample vial, to which 45 parts by weight of NVF, 20 partsby weight of tripropylene glycol diacrylate, 10 parts by weight ofglycerin ethylene oxide adduct triacrylate, 1.5 parts by weight ofIrgacure 819, 2.5 parts by weight of Irgacure 369 and 1 part by weightof Darocur EHA were added, followed by stirring with a magnetic stirrerfor 1 hour, to prepare a transparent ink composition 1 (T1).

2) Transparent Ink Composition 2 (T2): N-Vinylformamide 59 parts byweight (Beamset 770, produced by Arakawa Chemical Industries, Ltd.)Tripropylene glycol diacrylate 20 parts by weight (Aronix M-220,produced by Toagosei Co., Ltd.) Glycerin ethylene oxide adduct 10 partsby weight triacrylate (NK Ester A-Gly-3E, produced by Shin-nakamuraChemical Corp.) Irgacure 369 4.0 parts by weight (produced by CibaSpecialty Chemicals, Inc.) Darocur EHA 1.0 part by weight (produced byCiba Specialty Chemicals, Inc.) Polymerizable fine particles 1 6.0 partsby weightProduction Process of Transparent Ink Composition 2

20 parts by weight of the monomer solution B was placed in a 100-mLlight-shielded sample vial, to which 45 parts by weight of NVF, 20 partsby weight of tripropylene glycol diacrylate, 10 parts by weight ofglycerin ethylene oxide adduct triacrylate, 4.0 parts by weight ofIrgacure 369 and 1 part by weight of Darocur EHA were added, followed bystirring with a magnetic stirrer for 1 hour, to prepare a transparentink composition 2 (T2).

3) Transparent Ink Composition 3 (T3): N-Vinylformamide 59 parts byweight (Beamset 770, produced by Arakawa Chemical Industries, Ltd.)Tripropylene glycol diacrylate 20 parts by weight (Aronix M-220,produced by Toagosei Co., Ltd.) Glycerin ethylene oxide adduct 10 partsby weight triacrylate (NK Ester A-Gly-3E, produced by Shin-nakamuraChemical Corp.) Irgacure 819 4.0 parts by weight (produced by CibaSpecialty Chemicals, Inc.) Darocur EHA 1.0 part by weight (produced byCiba Specialty Chemicals, Inc.) Polymerizable fine particles 1 6.0 partsby weightProduction Process of Transparent Ink Composition 3

20 parts by weight of the monomer solution B was placed in a 100-mLlight-shielded sample vial, to which 45 parts by weight of NVF, 20 partsby weight of tripropylene glycol diacrylate, 10 parts by weight ofglycerin ethylene oxide adduct triacrylate, 4.0 parts by weight ofIrgacure 819 and 1 part by weight of Darocur EHA were added, followed bystirring with a magnetic stirrer for 1 hour, to prepare a transparentink composition 3 (T3).

4) Transparent Ink Composition 4 (T4): N-Vinylformamide 59 parts byweight (Beamset 770, produced by Arakawa Chemical Industries, Ltd.)Tripropylene glycol diacrylate 20 parts by weight (Aronix M-220,produced by Toagosei Co., Ltd.) Glycerin ethylene oxide adduct 10 partsby weight triacrylate (NK Ester A-Gly-3E, produced by Shin-nakamuraChemical Corp.) Irgacure 819 2.0 parts by weight (produced by CibaSpecialty Chemicals, Inc.) Irgacure 369 2.0 parts by weight (produced byCiba Specialty Chemicals, Inc.) Darocur EHA 1.0 part by weight (producedby Ciba Specialty Chemicals, Inc.) Polymerizable fine particles 1 6.0parts by weightProduction Process of Transparent Ink Composition 4

20 parts by weight of the monomer solution B was placed in a 100-mLlight-shielded sample vial, to which 45 parts by weight of NVF, 20 partsby weight of tripropylene glycol diacrylate, 10 parts by weight ofglycerin ethylene oxide adduct triacrylate, 2.0 parts by weight ofIrgacure 819, 2.0 parts by weight of Irgacure 369 and 1 part by weightof Darocur EHA were added/followed by stirring with a magnetic stirrerfor 1 hour, to prepare a transparent ink composition 4 (T4).

5) Transparent Ink Composition 5 (T5): N-Vinylformamide 59 parts byweight (Beamset 770, produced by Arakawa Chemical Industries, Ltd.)Tripropylene glycol diacrylate 20 parts by weight (Aronix M-220,produced by Toagosei Co., Ltd.) Glycerin ethylene oxide adduct 10 partsby weight triacrylate (NK Ester A-Gly-3E, produced by Shin-nakamuraChemical Corp.) Darocur 1173 4.0 parts by weight (produced by CibaSpecialty Chemicals, Inc.) Darocur EHA 1.0 part by weight (produced byCiba Specialty Chemicals, Inc.) Polymerizable fine particles 1 6.0 partsby weightProduction Process of Transparent Ink Composition 5

20 parts by weight of the monomer solution B was placed in a 100-mLlight-shielded sample vial, to which 45 parts by weight of NVF, 20 partsby weight of tripropylene glycol diacrylate, 10 parts by weight ofglycerin ethylene oxide adduct triacrylate, 4.0 parts by weight ofDarocur 1173 and 1 part by weight of Darocur EHA were added, followed bystirring with a magnetic stirrer for 1 hour, to prepare a transparentink composition 4 (T5).

Darocur 1173 had substantially no absorption at a wavelength of 365 nmor more, and corresponds neither to an interior curablephotopolymerization initiator nor a surface curable photopolymerizationinitiator.

6) Transparent Ink Composition 6 (T6): N-Vinylformamide 65 parts byweight (Beamset 770, produced by Arakawa Chemical Industries, Ltd.)Tripropylene glycol diacrylate 20 parts by weight (Aronix M-220,produced by Toagosei Co., Ltd.) Glycerin ethylene oxide adduct 10 partsby weight triacrylate (NK Ester A-Gly-3E, produced by Shin-nakamuraChemical Corp.) Darocur 1173 4.0 parts by weight (produced by CibaSpecialty Chemicals, Inc.) Darocur EHA 1.0 part by weight (produced byCiba Specialty Chemicals, Inc.)Production Process of Transparent Ink Composition 6

65 parts by weight of NVF, 20 parts by weight of tripropylene glycoldiacrylate, 10 parts by weight of glycerin ethylene oxide adducttriacrylate, 4.0 parts by weight of Darocur 1173 and 1 part by weight ofDarocur EHA were placed in a 100-mL light-shielded sample vial andstirred with a magnetic stirrer for 1 hour to prepare a transparent inkcomposition 6 (T6).

The chemical names of the commercially available compounds are asfollows.

-   Darocur EHA: 2-ethylhexyl-4-dimethylaminobenzoate-   Darocur 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one

The white ink compositions 1 to 4 (W1 to W4, ink composition A) and thetransparent ink compositions 1 to 6 (T1 to T6, ink composition B) areshown in Table 1. The combinations of W1 to W4 and T1 to T6 used inExamples 1 to 8, Reference Examples 1 to 8, and Comparative Examples 1to 24 are shown in Table 2.

TABLE 1 Ink compositions A and B used in Examples 1-8, ReferenceExamples 1-8 and Comparative Examples 1-24 White ink composition (A)Transparent ink composition (B) W1 W2 W3 W4 T1 T2 T3 T4 T5 T6 Titaniumdioxide fine particles (B) 6 6 6 6 — — — — — (white colorant)N-vinylformamide 60 60  60  60  59 59 59 59  59 65 (polymerizablecompound, monofunctional monomer) Tripropylene glycol diacrylate 30 29 29  29  20 20 20 20  20 20 (polymerizable compound, bifunctionalmonomer) Glycerin EO adduct triacrylate — — — — 10 10 10 10  10 10(polymerizable compound, polyfunctional monomer) Irgacure 819 2.5 4 — 21.5 —  4 2 — — (interior curable photopolymerization initiator) Irgacure369 0.5 — 4 2 2.5  4 — 2 — — (surface curable photopolymerizationinitiator) Darocur 1173 — — — — — — — —  4  4 (photopolymerizationinitiator) Darocur EHA 1 1 1 1 1  1  1 1  1  1 (polymerizationaccelerator) Polymerizable fine particles 1 — — — — 6  6  6 6  6 —(polymerization accelerator) (Note: % by weight)

TABLE 2 Examples 1 to 8, Reference Examples 1-8 and Comparative Examples1-24 White Irradi- ink Transparent ating compo- ink Curing device sitioncomposition property Note Example 1 1 W1 T1 A — Example 2 1 W1 T2 A —Example 3 1 W2 T1 A — Example 4 1 W2 T2 A — Example 5 2 W1 T1 A —Example 6 2 W1 T2 A — Example 7 2 W2 T1 A — Example 8 2 W2 T2 A —Comparative 2 W3 T1 B interior curing Example 1 failure Comparative 2 W3T2 B interior curing Example 2 failure Comparative 1 W3 T1 B interiorcuring Example 3 failure Comparative 1 W3 T2 B interior curing Example 4failure Comparative 2 W1 T3 B surface Example 5 unevenly curedComparative 2 W2 T3 B surface Example 6 unevenly cured Comparative 1 W1T3 B surface curing Example 7 failure Comparative 1 W2 T3 B surfacecuring Example 8 failure Reference 2 W4 T1 B interior curing Example 1failure Reference 2 W4 T2 B interior curing Example 2 failure Reference1 W4 T1 B interior curing Example 3 failure Reference 1 W4 T2 B interiorcuring Example 4 failure Reference 2 W1 T4 B surface Example 5 unevenlycured Reference 2 W2 T4 B surface Example 6 unevenly cured Reference 1W1 T4 B surface curing Example 7 failure Reference 1 W2 T4 B surfacecuring Example 8 failure Comparative 2 W1 T5 B surface curing Example 9failure Comparative 2 W2 T5 B surface curing Example 10 failureComparative 2 W3 T5 C completely not Example 11 cured Comparative 2 W4T5 C completely not Example 12 cured Comparative 1 W1 T5 B surfacecuring Example 13 failure Comparative 1 W2 T5 B surface curing Example14 failure Comparative 1 W3 T5 C completely not Example 15 curedComparative 1 W4 T5 C completely not Example 16 cured Comparative 2 W1T6 B surface curing Example 17 failure Comparative 2 W2 T6 B surfacecuring Example 18 failure Comparative 2 W3 T6 B surface curing Example19 failure Comparative 2 W4 T6 B surface curing Example 20 failureComparative 1 W1 T6 B surface curing Example 21 failure Comparative 1 W2T6 B surface curing Example 22 failure Comparative 1 W3 T6 B surfacecuring Example 23 failure Comparative 1 W4 T6 B surface curing Example24 failure

Examples 9 and 10, Reference Examples 9 to 12, and Comparative Examples25 to 36

Examples 9 and 10, Reference Examples 9 to 12, and Comparative Examples25 to 36 shown in Table 4 below are all examples using the inkcomposition sets containing color ink compositions (Sets 1 to 3, inkcomposition A) and the transparent ink compositions (T1 to T6, inkcomposition B).

Irgacure 819 (an interior curable photopolymerization initiator,produced by Ciba Specialty Chemicals, Inc.) and Irgacure 369 (a surfacecurable photopolymerization initiator, produced by Ciba SpecialtyChemicals, Inc.) are used as photopolymerization initiators mixed withthe color ink compositions (Sets 1 to 3, ink composition A) and specificexamples of the ink composition A, but the invention is not limitedthereto. Irgastab UV-10 (produced by Ciba Specialty Chemicals, Inc.) isused as a thermal polymerization inhibitor, but the invention is notlimited thereto.

1. Color Ink Composition (Ink Composition A: Ink Composition Containingat Least Colorant and Photopolymerization Initiator)

1) Preparation of Color Ink Compositions 1 to 4 (Color Ink Set 1):

An ink composition 1 having the following formulation was prepared. Thepreparation was carried out in the following manner. 15 parts of apigment, 1 part of a dispersant and 84 parts of N-vinylformamide(hereinafter, abbreviated as NVF) were mixed and stirred to obtain amixture, which was then dispersed in a sand mill (produced by YasukawaManufacturing Co., Ltd.) along with zirconia beads (diameter: 1.5 mm)for 6 hours. Thereafter, the zirconia beads were separated with aseparator to obtain a pigment dispersion liquid C.

The solvents and additives of the following formulation except for thepigment and the dispersant were then mixed and completely dissolved toprepare an ink solvent, to which the pigment dispersion liquid C wasgradually added dropwise under stirring, and after completing thedropwise addition, the mixture was stirred at ordinary temperature for30 minutes. Thereafter, the mixture was filtered with a 5-μm membranefilter to obtain a color ink composition 1. Color ink compositions 2 to4 were prepared in the same manner.

2-1) Color Ink Composition 1 (Y1) C.I. Pigment Yellow 155 (pigment) 3.0%by weight Polyoxyalkylene-added polyalkyleneamine 1.0% by weight(dispersant, Discol N-518, produced by Dai-ichi Kogyo Seiyaku Co., Ltd.)BYK-UV3570 0.5% by weight (polyester-modified silicone surfactant,produced by BYK Chemie Japan Co., Ltd.) NVF 20.0% by weight (produced byArakawa Chemical Industries, Ltd.) Allyl glycol 35.3% by weight(produced by Nippon Nyukazai Co., Ltd.) Tripropylene glycol diacrylate20.0% by weight (Aronix M-220, produced by Toagosei Co., Ltd.)Trimethylolpropane EO-modified 15.0% by weight triacrylate (Viscoat#360, produced by Osaka Organic Chemical Industry, Ltd.) Irgacure 8194.0% by weight (produced by Ciba Specialty Chemicals, Inc.) Irgacure 3691.0% by weight (produced by Ciba Specialty Chemicals, Inc.) IrgastabUV-10 0.2% by weight (produced by Ciba Specialty Chemicals, Inc.) 2-2)Color Ink Composition 2 (M1) C.I. Pigment Violet 19 (pigment) 3.0% byweight Polyoxyalkylene-added polyalkyleneamine 1.0% by weight(dispersant, Discol N-518, produced by Dai-ichi Kogyo Seiyaku Co., Ltd.)BYK-UV3570 0.5% by weight (polyester-modified silicone surfactant,produced by BYK Chemie Japan Co., Ltd.) NVF 20.0% by weight (produced byArakawa Chemical Industries, Ltd.) Allyl glycol 35.3% by weight(produced by Nippon Nyukazai Co., Ltd.) Tripropylene glycol diacrylate20.0% by weight (Aronix M-220, produced by Toagosei Co., Ltd.)Trimethylolpropane EO-modified 15.0% by weight triacrylate (Viscoat#360, produced by Osaka Organic Chemical Industry, Ltd.) Irgacure 8194.0% by weight (produced by Ciba Specialty Chemicals, Inc.) Irgacure 3691.0% by weight (produced by Ciba Specialty Chemicals, Inc.) IrgastabUV-10 0.2% by weight (produced by Ciba Specialty Chemicals, Inc.) 2-3)Color Ink Composition 3 (C1) C.I. Pigment Blue 15:3 (pigment) 3.0% byweight Polyoxyalkylene-added polyalkyleneamine 1.0% by weight(dispersant, Discol N-518, produced by Dai-ichi Kogyo Seiyaku Co., Ltd.)BYK-UV3570 0.5% by weight (polyester-modified silicone surfactant,produced by BYK Chemie Japan Co., Ltd.) NVF 20.0% by weight (produced byArakawa Chemical Industries, Ltd.) Allyl glycol 35.3% by weight(produced by Nippon Nyukazai Co., Ltd.) Tripropylene glycol diacrylate20.0% by weight (Aronix M-220, produced by Toagosei Co., Ltd.)Trimethylolpropane EO-modified 15.0% by weight triacrylate (Viscoat#360, produced by Osaka Organic Chemical Industry, Ltd.) Irgacure 8194.0% by weight (produced by Ciba Specialty Chemicals, Inc.) Irgacure 3691.0% by weight (produced by Ciba Specialty Chemicals, Inc.) IrgastabUV-10 0.2% by weight (produced by Ciba Specialty Chemicals, Inc.) 2-4)Color Ink Composition 4 (Bk1) C.I. Pigment Black 7 (pigment) 3.0% byweight Polyoxyalkylene-added polyalkyleneamine 2.0% by weight(dispersant, Discol N-518, produced by Dai-ichi Kogyo Seiyaku Co., Ltd.)BYK-UV3570 0.5% by weight (polyester-modified silicone surfactant,produced by BYK Chemie Japan Co., Ltd.) NVF 20.0% by weight (produced byArakawa Chemical Industries, Ltd.) Allyl glycol 34.3% by weight(produced by Nippon Nyukazai Co., Ltd.) Tripropylene glycol diacrylate20.0% by weight (Aronix M-220, produced by Toagosei Co., Ltd.)Trimethylolpropane EO-modified 15.0% by weight triacrylate (Viscoat#360, produced by Osaka Organic Chemical Industry, Ltd.) Irgacure 8194.0% by weight (produced by Ciba Specialty Chemicals, Inc.) Irgacure 3691.0% by weight (produced by Ciba Specialty Chemicals, Inc.) IrgastabUV-10 0.2% by weight (produced by Ciba Specialty Chemicals, Inc.)3) Preparation of Color Ink Compositions 5 to 8 (Color Ink Set 2):

Ink compositions having the following formulation were prepared. Thepreparation was carried out in the same manner as in the preparation ofthe color ink composition 1 except that the proportion of thepolymerization initiator was changed.

3-1) Color Ink Composition 5 (Y2) C.I. Pigment Yellow 155 (pigment) 3.0%by weight Polyoxyalkylene-added polyalkyleneamine 1.0% by weight(dispersant, Discol N-518, produced by Dai-ichi Kogyo Seiyaku Co., Ltd.)BYK-UV3570 0.5% by weight (polyester-modified silicone surfactant,produced by BYK Chemie Japan Co., Ltd.) NVF 24.0% by weight (produced byArakawa Chemical Industries, Ltd.) Lauryl methacrylate 31.3% by weight(produced by Mitsubishi Gas Chemical Co., Inc.) Tripropylene glycoldiacrylate 20.0% by weight (Aronix M-220, produced by Toagosei Co.,Ltd.) Trimethylolpropane EO-modified 15.0% by weight triacrylate(Viscoat #360, produced by Osaka Organic Chemical Industry, Ltd.)Irgacure 819 2.5% by weight (produced by Ciba Specialty Chemicals, Inc.)Irgacure 369 2.5% by weight (produced by Ciba Specialty Chemicals, Inc.)Irgastab UV-10 0.2% by weight (produced by Ciba Specialty Chemicals,Inc.) 3-2) Color Ink Composition 6 (M2) C.I. Pigment Violet 19 (pigment)3.0% by weight Polyoxyalkylene-added polyalkyleneamine 1.0% by weight(dispersant, Discol N-518, produced by Dai-ichi Kogyo Seiyaku Co., Ltd.)BYK-UV3570 0.5% by weight (polyester-modified silicone surfactant,produced by BYK Chemie Japan Co., Ltd.) NVF 24.0% by weight (produced byArakawa Chemical Industries, Ltd.) Lauryl methacrylate 31.3% by weight(produced by Mitsubishi Gas Chemical Co., Inc.) Tripropylene glycoldiacrylate 20.0% by weight (Aronix M-220, produced by Toagosei Co.,Ltd.) Trimethylolpropane EO-modified 15.0% by weight triacrylate(Viscoat #360, produced by Osaka Organic Chemical Industry, Ltd.)Irgacure 819 2.5% by weight (produced by Ciba Specialty Chemicals, Inc.)Irgacure 369 2.5% by weight (produced by Ciba Specialty Chemicals, Inc.)Irgastab UV-10 0.2% by weight (produced by Ciba Specialty Chemicals,Inc.) 3-3) Color Ink Composition 7 (C2) C.I. Pigment Blue 15:3 (pigment)3.0% by weight Polyoxyalkylene-added polyalkyleneamine 1.0% by weight(dispersant, Discol N-518, produced by Dai-ichi Kogyo Seiyaku Co., Ltd.)BYK-UV3570 0.5% by weight (polyester-modified silicone surfactant,produced by BYK Chemie Japan Co., Ltd.) NVF 24.0% by weight (produced byArakawa Chemical Industries, Ltd.) Lauryl methacrylate 31.3% by weight(produced by Mitsubishi Gas Chemical Co., Inc.) Tripropylene glycoldiacrylate 20.0% by weight (Aronix M-220, produced by Toagosei Co.,Ltd.) Trimethylolpropane EO-modified 15.0% by weight triacrylate(Viscoat #360, produced by Osaka Organic Chemical Industry, Ltd.)Irgacure 819 2.5% by weight (produced by Ciba Specialty Chemicals, Inc.)Irgacure 369 2.5% by weight (produced by Ciba Specialty Chemicals, Inc.)Irgastab UV-10 0.2% by weight (produced by Ciba Specialty Chemicals,Inc.) 3-4) Color Ink Composition 8 (Bk2) C.I. Pigment Black 7 (pigment)3.0% by weight Polyoxyalkylene-added polyalkyleneamine 2.0% by weight(dispersant, Discol N-518, produced by Dai-ichi Kogyo Seiyaku Co., Ltd.)BYK-UV3570 0.5% by weight (polyester-modified silicone surfactant,produced by BYK Chemie Japan Co., Ltd.) NVF 24.0% by weight (produced byArakawa Chemical Industries, Ltd.) Lauryl methacrylate 30.3% by weight(produced by Mitsubishi Gas Chemical Co., Inc.) Tripropylene glycoldiacrylate 20.0% by weight (Aronix M-220, produced by Toagosei Co.,Ltd.) Trimethylolpropane EO-modified 15.0% by weight triacrylate(Viscoat #360, produced by Osaka Organic Chemical Industry, Ltd.)Irgacure 819 2.5% by weight (produced by Ciba Specialty Chemicals, Inc.)Irgacure 369 2.5% by weight (produced by Ciba Specialty Chemicals, Inc.)Irgastab UV-10 0.2% by weight (produced by Ciba Specialty Chemicals,Inc.)4) Preparation of Color Ink Compositions 9 to 12 (Color Ink Set 3):

Ink compositions having the following formulation were prepared. Thepreparation was carried out in the same manner as in the preparation ofthe color ink composition 1 except that the polymerization initiator waschanged.

4-1) Color Ink Composition 9 (Y3) C.I. Pigment Yellow 155 (pigment) 3.0%by weight Polyoxyalkylene-added polyalkyleneamine 1.0% by weight(dispersant, Discol N-518, produced by Dai-ichi Kogyo Seiyaku Co., Ltd.)BYK-UV3570 0.5% by weight (polyester-modified silicone surfactant,produced by BYK Chemie Japan Co., Ltd.) NVF 24.0% by weight (produced byArakawa Chemical Industries, Ltd.) Lauryl methacrylate 31.3% by weight(produced by Mitsubishi Gas Chemical Co., Inc.) Tripropylene glycoldiacrylate 20.0% by weight (Aronix M-220, produced by Toagosei Co.,Ltd.) Trimethylolpropane EO-modified 15.0% by weight triacrylate(Viscoat #360, produced by Osaka Organic Chemical Industry, Ltd.)Irgacure 369 5.0% by weight (produced by Ciba Specialty Chemicals, Inc.)Irgastab UV-10 0.2% by weight (produced by Ciba Specialty Chemicals,Inc.) 4-2) Color Ink Composition 10 (M3) C.I. Pigment Violet 19(pigment) 3.0% by weight Polyoxyalkylene-added polyalkyleneamine 1.0% byweight (dispersant, Discol N-518, produced by Dai-ichi Kogyo SeiyakuCo., Ltd.) BYK-UV3570 0.5% by weight (polyester-modified siliconesurfactant, produced by BYK Chemie Japan Co., Ltd.) NVF 24.0% by weight(produced by Arakawa Chemical Industries, Ltd.) Lauryl methacrylate31.3% by weight (produced by Mitsubishi Gas Chemical Co., Inc.)Tripropylene glycol diacrylate 20.0% by weight (Aronix M-220, producedby Toagosei Co., Ltd.) Trimethylolpropane EO-modified 15.0% by weighttriacrylate (Viscoat #360, produced by Osaka Organic Chemical Industry,Ltd.) Irgacure 369 5.0% by weight (produced by Ciba Specialty Chemicals,Inc.) Irgastab UV-10 0.2% by weight (produced by Ciba SpecialtyChemicals, Inc.) 4-3) Color Ink Composition 11 (C3) C.I. Pigment Blue15:3 (pigment) 3.0% by weight Polyoxyalkylene-added polyalkyleneamine1.0% by weight (dispersant, Discol N-518, produced by Dai-ichi KogyoSeiyaku Co., Ltd.) BYK-UV3570 0.5% by weight (polyester-modifiedsilicone surfactant, produced by BYK Chemie Japan Co., Ltd.) NVF 24.0%by weight (produced by Arakawa Chemical Industries, Ltd.) Laurylmethacrylate 31.3% by weight (produced by Mitsubishi Gas Chemical Co.,Inc.) Tripropylene glycol diacrylate 20.0% by weight (Aronix M-220,produced by Toagosei Co., Ltd.) Trimethylolpropane EO-modified 15.0% byweight triacrylate (Viscoat #360, produced by Osaka Organic ChemicalIndustry, Ltd.) Irgacure 369 5.0% by weight (produced by Ciba SpecialtyChemicals, Inc.) Irgastab UV-10 0.2% by weight (produced by CibaSpecialty Chemicals, Inc.) 4-4) Color Ink Composition 12 (Bk3) C.I.Pigment Black 7 (pigment) 3.0% by weight Polyoxyalkylene-addedpolyalkyleneamine 2.0% by weight (dispersant, Discol N-518, produced byDai-ichi Kogyo Seiyaku Co., Ltd.) BYK-UV3570 0.5% by weight(polyester-modified silicone surfactant, produced by BYK Chemie JapanCo., Ltd.) NVF 24.0% by weight (produced by Arakawa Chemical Industries,Ltd.) Lauryl methacrylate 30.3% by weight (produced by Mitsubishi GasChemical Co., Inc.) Tripropylene glycol diacrylate 20.0% by weight(Aronix M-220, produced by Toagosei Co., Ltd.) TrimethylolpropaneEO-modified 15.0% by weight triacrylate (Viscoat #360, produced by OsakaOrganic Chemical Industry, Ltd.) Irgacure 369 5.0% by weight (producedby Ciba Specialty Chemicals, Inc.) Irgastab UV-10 0.2% by weight(produced by Ciba Specialty Chemicals, Inc.)

The ink sets 1 to 3 (Y1 to Y3, M1 to M3, C1 to C3, and Bk1 to Bk3) (inkcomposition A) are summarized in Table 3. The combinations used inExamples 9 and 10, Reference Examples 9 to 12, and Comparative Examples25 to 36, i.e., the combinations of the ink sets 1 to 3 (ink compositionA) and the transparent ink compositions T1 to T6 (ink composition B)used in Examples 1 to 8, Reference Examples 1 to 8, and ComparativeExamples 1 to 24, are shown in Table 4.

TABLE 3 Color ink set used in Examples 9-10, Reference Examples 9-12 andComparative Examples 25-36 Color ink set Set 1 Set 2 Set 3 Y1 M1 C1 Bk1Y2 M2 C2 Bk3 Y3 M3 C3 Bk3 C.I. Pigment Yellow 155 (colorant, yellowpigment) 3 — — — 3 — — — 3 — — — C.I. Pigment Violet 19 (colorant,magenta pigment) — 3 — — — 3 — — — 3 — — C.I. Pigment Blue 15:3(colorant, cyan pigment) — — 3 — — — 3 — — — 3 — C.I. Pigment black 7(colorant, black pigment) — — — 3 — — — 3 — — — 3 Polyoxyalkylene-addedpolyalkyleneamine 1 1 1 2 1 1 1 2 1 1 1 2 (dispersant) BYK-UV3570(surfactant) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5N-vinylformamide (NVF) 20 20 20 20 24 24 24 24 24 24 24 24(polymerizable compound, monofunctional monomer) Lauryl methacrylate — —— — 31.3 31.3 31.3 30.3 31.3 31.3 31.3 30.3 (polymerizable compound,monofunctional monomer) Allyl glycol 35.3 35.3 35.3 34.3 — — — — — — — —(polymerizable compound, monofunctional monomer) Tripropylene glycoldiacrylate 20 20 20 20 20 20 20 20 20 20 20 20 (polymerizable compound,bifunctional monomer) Trimethylolpropane EO-modified triacrylate 15 1515 15 15 15 15 15 15 15 15 15 (polymerizable compound, polyfunctionalmonomer) Irgacure 819 (interior curable 4 4 4 4 2.5 2.5 2.5 2.5 — — — —photopolymerization initiator) Irgacure 369 (surface curable 1 1 1 1 2.52.5 2.5 2.5 5 5 5 5 photopolymerization initiator) Irgastab UV-10(thermal polymerization inhibitor) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 02 0.2 020.2 0.2 (Note: % by weight)

TABLE 4 Color ink composition Transparent ink composition Curingproperty Example 9 Set 1 (Y1 + M1 + C1 + Bk1) T1 A Example 10 Set 1(Y1 + M1 + C1 + Bk1) T2 A Comparative Example 25 Set 1 (Y1 + M1 + C1 +Bk1) T3 B Reference Example 9 Set 1 (Y1 + M1 + C1 + Bk1) T4 BComparative Example 26 Set 1 (Y1 + M1 + C1 + Bk1) T5 B ComparativeExample 27 Set 1 (Y1 + M1 + C1 + Bk1) T6 B Reference Example 10 Set 2(Y2 + M2 + C2 + Bk2) T1 B Reference Example 11 Set 2 (Y2 + M2 + C2 +Bk2) T2 B Comparative Example 28 Set 2 (Y2 + M2 + C2 + Bk2) T3 BReference Example 12 Set 2 (Y2 + M2 + C2 + Bk2) T4 B Comparative Example29 Set 2 (Y2 + M2 + C2 + Bk2) T5 C Comparative Example 30 Set 2 (Y2 +M2 + C2 + Bk2) T6 B Comparative Example 31 Set 3 (Y3 + M3 + C3 + Bk3) T1B Comparative Example 32 Set 3 (Y3 + M3 + C3 + Bk3) T2 B ComparativeExample 33 Set 3 (Y3 + M3 + C3 + Bk3) T3 B Comparative Example 34 Set 3(Y3 + M3 + C3 + Bk3) T4 B Comparative Example 35 Set 3 (Y3 + M3 + C3 +Bk3) T5 C Comparative Example 36 Set 3 (Y3 + M3 + C3 + Bk3) T6 B

The following Printing Test 1 (curing test) was carried out for Examples1 to 8, Reference Examples 1 to 8, and Comparative Examples 1 to 24. Theevaluation results are shown in Table 2.

Printing Test 1: Curing Test

An ink-jet printer (PM-G900, produced by Seiko Epson Corp.) was used.The ink compositions were charged in separate nozzle rows according tothe combinations shown in Table 1 below, and a solid pattern was printedunder such conditions that the ink compositions were simultaneouslyejected under ordinary temperature and ordinary pressure. The printingconditions were set in such a manner that the white ink composition (inkcomposition A) was attached to a recording medium, and thereafter thetransparent ink composition (ink composition B) was attached to therecording medium. An OHP film of A4 size (XEROX FILM (without frame),produced by Fuji Xerox Co., Ltd.) was used as the recording medium. Therecording medium was then subjected to printing and curing treatmentswith an ultraviolet ray irradiating device provided at a paper deliveryoutlet. The curing property was evaluated visually.

The following two kinds of ultraviolet ray irradiating devices were usedin the test.

-   Irradiating Device 1:

Light source: UV LED UCCU033 (produced by Nichia Corp.)

Output power: 100 mW

Peak wavelength: 365 nm

Irradiation condition: 22 mW/cm²

Accumulated light amount: 264 mJ/cm²

-   Irradiating Device 2:

Light source: UV LED US365D (produced by Nitride Semiconductors Co.,Ltd.)

Output power: 2 mW

Peak wavelength: 365 nm

Irradiation condition: 1.5 mW/cm²

Accumulated light amount: 90 mJ/cm²

Evaluation Standard of Curing Property

-   -   A: Both the surface and the interior were completely cured.    -   B: Only the surface was cured, but the interior was in a liquid        state; only the interior was cured, but the surface was not        cured; or the surface was separated to a cured part and an        uncured part to form an uneven state.    -   C: The compositions were not cured but remained in a liquid        state.

The following Printing Test 2 (curing test) was carried out for Examples9 and 10, Reference Examples 9 to 12, and Comparative Examples 25 to 36.The evaluation results are shown in Table 4.

Printing Test 2; Curing Test

An ink-jet printer (PM-G900, produced by Seiko Epson Corp.) was used.The ink compositions were charged in separate nozzle rows according tothe combinations shown in Table 4, and the transparent ink compositionswere charged in a GO row. A full color image was printed under suchconditions that the ink compositions were simultaneously ejected underordinary temperature and ordinary pressure. An OHP film of A4 size(XEROX FILM (without frame), produced by Fuji Xerox Co., Ltd.) was usedas the recording medium. The recording medium was then subjected toprinting and curing treatments with an ultraviolet ray irradiatingdevice 1 provided at a paper delivery outlet under such curingconditions that the accumulated light amount at 365 nm was 1,320 mJ/cm².The curing property was evaluated visually in the same manner as above.

While the present invention has been described in detail and withreference to specific embodiments thereof, it will be apparent to oneskilled in the art that various changes and modifications can be madetherein without departing from the spirit and scope thereof.

This application is based on Japanese Patent Application Nos.2004-298544 and 2005-296049.

1. An ink-jet recording method comprising the steps of: (a) preparing anink composition set comprising (i) an ink composition A comprising atleast a colorant and an interior curable photopolymerization initiator,wherein the interior curable photopolymerization initiator contained inthe ink composition A comprises an acylphosphine oxide as a majorcomponent contained in an amount of 60% by weight or more based on thephotopolymerization initiator in the ink composition A and (ii) an inkcomposition B comprising at least a polymerizable compound, a surfacecurable photopolymerization initiator and a polymerization accelerator,wherein the surface curable photopolymerization initiator contained inthe ink composition B comprises an α-aminoketone as a major componentcontained in an amount of 60% by weight or more based on thephotopolymerization initiator in the ink composition B; (b) attachingthe ink composition A and the ink composition B to a recording medium by(i) ejecting the ink composition A to form a first, colorant layer onthe recording medium; and then (ii) ejecting the ink composition B toform a second layer on the colorant layer formed in step (b) (i); and(c) irradiating the ejected compositions with an ultraviolet ray to forman image through ultraviolet ray curing.
 2. The ink-jet recording methodas claimed in claim 1, wherein the polymerization accelerator comprisesfine particles having a polymerizable functional group.
 3. The ink-jetrecording method as claimed in claim 1, wherein the ink composition B isa transparent ink composition and the colorant contained in the inkcomposition A is a pigment.
 4. An ink composition set comprising (a) anink composition A comprising at least a colorant and an interior curablephotopolymerization initiator, wherein the interior curablephotopolymerization initiator contained in the ink composition Acomprises an acylphosphine oxide as a major component contained in anamount of 60% by weight or more based on the photopolymerizationinitiator of the ink composition A; and (b) an ink composition Bcomprising at least a polymerizable compound, a surface curablephotopolymerization initiator and a polymerization accelerator, whereinthe surface curable photopolymerization initiator contained in the inkcomposition B comprises an a-aminoketone as a major component containedin an amount of 60% by weight or more based on the photopolymerizationinitiator in the ink composition B.